title: New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization.
abstract: Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I(-), Br(-), Cl(-)).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3](4+)(PF6(-))4, [4](2+)(PF6(-))2, and [5](4+)(PF6(-))4 for the electro-crystallized products.
authors.affiliation: Department of Chemistry, Sultan Qaboos University , P.O. Box 36, Al-Khodh 123, Sultanate of Oman.
authors.forename: Hakikulla H
authors.initials: HH
authors.lastname: Shah
authors.forename: Rayya A
authors.initials: RA
authors.lastname: Al-Balushi
authors.forename: Mohammed K
authors.initials: MK
authors.lastname: Al-Suti
authors.forename: Muhammad S
authors.initials: MS
authors.lastname: Khan
authors.forename: Christopher H
authors.initials: CH
authors.lastname: Woodall
authors.forename: Anna L
authors.initials: AL
authors.lastname: Sudlow
authors.forename: Paul R
authors.initials: PR
authors.lastname: Raithby
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Köhn
authors.forename: Kieran C
authors.initials: KC
authors.lastname: Molloy
authors.forename: Frank
authors.initials: F
authors.lastname: Marken